US6365687B1 - Process for the polymerization and copolymerization of certain unsaturated hydrocarbons - Google Patents
Process for the polymerization and copolymerization of certain unsaturated hydrocarbons Download PDFInfo
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- US6365687B1 US6365687B1 US07/883,912 US88391292A US6365687B1 US 6365687 B1 US6365687 B1 US 6365687B1 US 88391292 A US88391292 A US 88391292A US 6365687 B1 US6365687 B1 US 6365687B1
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- 0 *C([H])C([H])([H])C(*)([H])C([H])([H])C(*)([H])C([H])([H])C(*)[H] Chemical compound *C([H])C([H])([H])C(*)([H])C([H])([H])C(*)([H])C([H])([H])C(*)[H] 0.000 description 3
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/14—Monomers containing five or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/04—Fractionation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/907—Specified means of reacting components of transition metal catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/09—Polyolefin
Definitions
- This invention relates to a process for polymerizing unsaturated hydrocarbons of the formula
- R is a saturated aliphatic, an alicyclic or an aromatic radical, alone, in mixture with one another, or in mixtures with small amounts, up to about 5%, of a monomer polymerizable therewith.
- the initial polymerization products obtained by the present method are mixtures of linear, head-to-tail amorphous and crystalline polymers having no branches longer than R.
- the polymers can be separated from the polymerizate by fractional dissolution.
- the crystalline polymers may comprise as nigh as 30% or even up to 55% of the mixture and have high molecular weights and fiber forming properties.
- the amorphous polymers may also have relatively high molecular weights and may exhibit rubber-like properties.
- the catalytic heavy metal compounds we use in preparing the catalyst for the polymerization of the alpha-olefins to polymers having the steric structures described below are halides of heavy metal selected from the sub-group of Groups IV to VI of the Periodic Table, including thorium, and uranium, i.e., halides of the elements of titanium, zirconium, hafnium, thorium, vanadium, tantalum, niobium, chromium, molybdenum, tungsten and uranium. These are metals belonging to Groups IVa, Va and VIa of the Mendeleeff Periodic Table.
- the catalytic metal alkyl compounds we use in preparing our catalyst are alkyl compounds of elements selected from the group forming the 2nd and 3rd columns of the Periodic Table, i.e., beryllium, magnesium, zinc, cadmium and other elements of the 2nd group, as well as boron, aluminum and other elements of the 3rd group.
- valences of the aforesaid elements are linked to the same or different alkyl radicals such as ethyl, propyl, butyl, etc.
- One valence of the element may be satisfied by halogen, or alkoxy radicals.
- the polymerization aids obtained by reacting heavy metal compounds and metal alkyl compounds in a solvent inert to the polymer to be formed were found useful in the production of high polymers of ethylene, it was not apparent that those agents would be useful in the polymerization of the unsaturated hydrocarbons containing the vinyl group.
- Processes and polymerization promoters that are useful for producing polyethylene of high molecular weight are not necessarily useful for producing high molecular weight polymers of the higher homologues of ethylene, such as, for instance, propylene.
- the products obtained by polymerizing the higher ethylene homologues by processes known in the art generally consist of mixtures of polymeric homologues containing variously branched isomers.
- Polymers of olefins in which one of. the hydrogen atoms of a CH 2 group is replaced by a CH 3 group, are usually non-crystalline, owing to stereochemical irregularity.”
- the new polymerization products are obtained by polymerizing monomeric material comprising at least one of the vinyl hydrocarbons containing three or more carbon atoms per molecule in the presence of polymerization aids obtained by reacting the heavy metal halide and metal alkyl compound in molar ratios such that the metal alkyl component is not more than ten times the heavy metal halide and is preferably less than five times the heavy metal halide, as will be seen from the examples given hereinafter.
- the catalyst is the reaction product of (a) a chloride of titanium with (b) an alkyl aluminum compound in which at least two of the valences of aluminum are satisfied by alkyl groups, and in which the third valence can be satisfied by alkyl or halide.
- the catalyst may also be the reaction product of (a) a chloride of titanium with (b) an aluminum trialkyl compound, in which the alkyl groups have up to four carbons each.
- an inert solvent preferably a saturated hydrocarbon solvent. This insures that the reaction proceeds smoothly, without violence, and without a strong temperature increase which would be considerable if the catalyst were used without prior dilution thereof.
- Solvents suitable for use in preparing the polymerization catalyst are paraffinic hydrocarbons such as, for instance, a light gasoline, (substantially free of olefinic bonds), n-heptane, iso-octane, and other substances preferably of the non-aromatic type. However, benzene has also been used.
- the solvents selected should preferably have boiling points lower than 150° C. and not swell the highest molecular weight polymers obtained.
- the heavy metal halide and metal alkyl compound may be dissolved separately in a solvent of the same group, and the solutions then brought together maintaining a low temperature, preferably a temperature somewhat below room temperature, such as 0° C. to 20° C.
- the solution of the heavy metal halide is added dropwise to the cooled solution of the metal alkyl compound.
- composition thus obtained may be further diluted with solvent and introduced into an autoclave for instance of the oscillating stainless steel type.
- the autoclave should be previously thoroughly dried and evacuated because it is of general advantage to carry out the entire process in the absence of oxygen and water.
- oxygen and water should be limited to small quantities, i.e., impurities, because they will consume a part of the metal alkyl component.
- the vinyl hydrocarbon or mixture containing it is preferably dried carefully and then pumped into the autoclave either in the liquid or gaseous phase, or as a mixture of both phases.
- the monomeric material is heated to a temperature below 120° C., and preferably to a temperature between 50 and 100° C.
- the pressure applied in the autoclave is preferably held between normal atmospheric pressure and 30 atmospheres, i.e., a relatively low pressure is used compared with that applied in other polymerization processes.
- the polymerization can be carried out at a temperature between 50 and 100° C. and more specifically between 60 and 70° C. for the polymerization of propylene.
- the upper limit for the temperature range is determined by the fact that at temperatures substantially above 100° C.
- the vinyl hydrocarbon or mixture may be pumped in one or several batches.
- the polymerization lasts for several hours up to several days, the autoclave being kept in motion until the decrease of pressure ceases.
- the gaseous phase above the reaction product is then vented, and the reaction product consisting of a solid mass is worked up.
- the reaction mass contains, as impurities, inorganic compounds originating from the decomposition of the catalyst as well as residual catalyst itself.
- the product is, therefore, treated with a suitable agent, for instance methanol, for decomposing the residual catalyst, and the product which is still soaked with the inert solvent and, say, methanol, then contains
- inorganic compounds e.g., of Al and Ti.
- This mass may be treated with isopropyl ether to dissolve the amorphous polymers; a dark suspension of the crystalline polymer including the inorganic compounds remains. By bubbling HCl through, the inorganic compounds are dissolved and the suspension becomes white. (The crystalline polymer remains undissolved.) By adding additional methanol, most of the dissolved amorphous polymer is precipitated. The purified polymer mixture is separated by filtration from the solvent mixture.
- the initial polymerization product is, as has been stated, a mixture of polymers. It comprises, usually, a small amount of an oily low molecular weight fraction, an amorphous fraction of higher molecular weight, and a high molecular weight fraction, the amorphous and crystalline polymers making up the bulk, generally, of the mixture.
- the products are thus mainly made up of polymers that can be classified in two types, not crystallizable, amorphous and crystalline.
- the mixtures can be used as such for various purposes, or the different fractions can be separated depending on their solubility in various solvents; the fractions varying in their amorphous and crystalline contents, in average molecular weights, and specific viscosity.
- the molecular weight of the products was estimated from specific viscosity measurements in tetrahydro-naphthalene solutions at a polymer concentration of 0.1 gm. per 100 gms. of solvent and from intrinsic viscosity measurements.
- Specific viscosity is the viscosity of the solution less the viscosity of the solvent, divided by the viscosity of the solvent.
- intrinsic viscosity is meant the limit of the ratio between specific viscosity and concentration for concentrations tending to zero ( Limit C ⁇ 0 ⁇ ⁇ ⁇ spec ⁇ C ,
- C is the concentration of the solution in gms/cs.).
- Products having an average molecular weight above 20,000 and up to 400,000 and higher may be obtained.
- the products are initially, and as has been stated, mixtures of polymers.
- mixtures comprise polymers which, depending on their steric structure, and their molecular weight, have very different characteristics.
- the amorphous products have viscous elastic properties comprised between those of a highly viscous liquid and those of an unvulcanized, non-crystallizable elastomer, while the solid, highly crystalline products, which can be oriented by drawing, give products of fiber-like behaviour.
- Both types of polymers are, as shown by their infra-red spectra, linear; in the case of polypropylene, e.g., both amorphous and crystalline polymers have similar infra-red spectra which are completely different from the infra-red spectra of the known branched polypropylene in which the branches are longer than R.
- the asymmetric C atom has a 1 configuration, and in the other a d configuration.
- the polymer may be considered as a copolymer of the two types of structural units, and therefore, if the substituent R is much larger than a H atom, is substantially non-crystalline and does not show any 1st order transition point.
- the cell contains 6 chain portions containing each 3 monomeric units.
- each stretch of principal chain included in the elementary cell corresponds to 3 monomeric units (—CH 2 —CHR—), and, that therefore a regular succession of monomeric units having alternatively d and 1 asymmetric carbon atoms can be excluded.
- a regular succession of monomeric units having alternatively d and 1 asymmetric carbon atoms can be excluded.
- the most probable is the one in which, at least for long portions of the main chain, all the asymmetric C atoms have the same steric configuration:
- the partially isotactic polymers produced and isolated from the crude polymerizates by us such as the partially crystalline fraction described in, for instance, Examples 1 and 2 below, comprise macromolecules consisting of sections having the Natta isotactic structure and sections having the Natta non-isotactic or atactic structure.
- the isotactic structure imparts to the product properties not previously known for any hydrocarbon.
- these products with a high molecular weight are, at room temperature, crystalline solids very different, e.g., from the elastomers obtained by known methods from isobutylene, which are crystallizable under stress and show a spiral-like linear chain, but with a different identity period.
- the substantial differences in the physical properties of the two types of polymers prepared by the present process are summarized in Table 2.
- solubilities of the two types of polymer permit of their easy separation by extraction with suitable solvents.
- the crystalline products always show a much lower solubility than the amorphous products independently from the molecular weight, while the solubilities of polymers of the same type, but having different molecular weight, decrease slightly and gradually with an increase of the molecular weight.
- the polypropylene products which are insoluble in boiling n-heptane and having a higher molecular weight than those previously mentioned, probably above 100,000 (intrinsic viscosity above 3), are solids having a density between 0.90 and 0.94, and a high melting point (about 160° C).
- a density of about 0.94 is the upper limit for a completely crystalline product. Said density was calculated from reticular distances determined from X-rays diffraction patterns of fibers. The specific gravity is lowered by the presence of an amorphous portion and in fact the amorphous ethersoluble polymers have a density lower than 0.90.
- the polypropylene products do not change directly into a flowing liquid, but retain the characteristics of an amorphous plastic substance. They can, therefore, be readily processed (at a temperature somewhat higher than the temperature of complete disappearance of the crystalline structure) by the methods (moulding, injection, extrusion) known for plastic materials. It is found, moreover, that these propylene polymers of Example I of very high molecular weight, with intrinsic viscosity above 3, having a high degree of crystallinity which is preserved up to relatively high temperatures (above 150° C.), show surprising mechanical characteristics, as will be further described, not previously accertained for any known hydrocarbon so that they can be satisfactorily employed in making textile fibers.
- the propylene polymers with very high molecular weight obtained by the instant method may be molded at temperatures higher than 130-150° C. to obtain plates, which are transparent when the product is well purified. Such plates may be cold stretched up to about 700%; the breaking load, referred to the section resulting after stretching, may be, e.g. for the product obtained according to Example II, higher than 30 kg/sq. mm., and even considerably higher if the product is drawn into thin filaments.
- the stretched filaments show a silk-like appearance and their good mechanical characteristics (high breaking load and high elongation at rupture of the stretched filament) make them particularly suitable for producing textile fibers.
- the polymer In order to remove the inorganic compounds originating from the decomposition of the catalyst, the polymer is suspended in di-isopropylether and the suspension is heated while strongly stirring and bubbling through gaseous HC1. After four hours a little methanol is added to the suspension in order to precipitate the polymer which might have been dissolved, and which is then filtered under suction.
- the polymer after being dried at 100° C. under reduced pressure, weighs 180 g. and has an ash content of 0.22%.
- This product containing a very wide range of propylene polymers, appears as a white, spongy solid, which at 140° C. has a transparent rubber-like appearance and at 155° C. is definitely melted. It can be moulded at 130° C. to flexible sheets which by X-ray diffraction patterns are shown to contain amorphous and crystalline portions. From the filtered liquid after distillation of the solvent a few grams of a very viscous oil are recovered.
- the solid polymer mixture obtained is extracted in succession with boiling acetone, ethyl ether and n-heptane in an extractor of the Kumagawa type and for each solvent the extraction is continued until the percolating solvent does not contain any appreciable quantities of extracted polymer.
- the acetone extract consists of oily, low molecular weight products and amounts to 2.8% of the solid polymer obtained.
- the n-heptane extract corresponding to 19% of the total polymer, after evaporation of the solvent in vacuum has an intrinsic viscosity of 1.2-1.3 and is, at room temperature, a partially crystalline solid, completely melted at 150°, which also shows the properties of an elastomer, however up to higher temperatures than the preceding fraction.
- the residue insoluble in the three solvents of Example I has a specific gravity of about 0.92, and an intrinsic viscosity determined in tetrahydronaphthalene solution of 3.33 (100 ml/g).
- a 1% solution in tetralin shows a specific viscosity of 0.374.
- the polymerization product By carrying out the polymerization of propylene in the presence of a polymerization agent prepared by reacting in the cold and in the absence of any olefin, tripropyl aluminum with titanium tetrachloride, the polymerization product has a much higher average molecular weight, as described in the following example.
- the acetone extract corresponds to 27.6% of the total and comprises semi-solid products of low molecular weight.
- the ether extract corresponds to 26.9% of the total and comprises a solid product of gummy appearance having an intrinsic viscosity of 1.57 (molecular weight about 63,000).
- the heptane extract corresponds to 15.1% of the obtained polymer and consists of partially crystalline polypropylene having an intrinsic viscosity of 2.36 (molecular weight about 120,000).
- the extraction residue comprises highly crystalline polypropylene having an intrinsic viscosity of 5.1 (molecular weight approximately 390,000).
- the obtained product may be easily oriented by hot drawing.
- the polymer mixture may be extruded to form filaments which, after cold stretching, show good mechanical properties.
- the polymerization was carried out as in the foregoing Example I, however in the cold (temperature 20° C.), by introducing in the autoclave 167 g. propylene, obtaining pressures of 3.0-3.6 atm.
- the polymerization is much slower and less complete. In fact, only 32 g. of polymer were obtained, of which 21 g. consisted of solid polymer.
- the solid polymer obtained is extractable for 7% with acetone in the heat, for 40.5% with ether and for 28% with heptane. After said extractions, 24% of the polymer obtained remains as residue.
- the fractions thus obtained have properties similar to those described in the preceding example.
- Example II After preparing the initiator as described in Example I and introducing the same in the autoclave, the latter is charged with one single batch of 270 grams of propylene. The temperature is maintained between 60 and 70° C. and the autoclave is kept in motion until pressure has decreased from an initial 15 to about 11 atmospheres. The gases vented from the autoclave after polymerization has terminated, contain 97.4 liters of propylene and 0.4 liter of ethylene. 3.5 liters of propylene and 0.5 liter of ethylene are evolved by the decomposition of the catalyst which is carried out as in Example I. 83 g. of polymer were obtained, which was purified as in Example I.
- the acetone extract of the polymer obtained amounts to 7.1% and consists of oily products.
- the ether extract corresponds to 43.9% and consists of an amorphous solid substance having in tetralin solution an intrinsic viscosity equal to 10.
- the heptane extract corresponds to 17.8% and consists of a partially crystalline solid having an intrinsic viscosity of 1.31.
- the residue which remains after said extractions corresponds to 31.2% and consists of a highly crystalline solid having a first order transition point of about 160° C. and an intrinsic viscosity in tetralin at 135° C. equal to 3.
- a second batch of 21 grams propylene is then introduced, with pressure rising to 28 atmospheres and again decreasing gradually to 15 atmospheres, whereupon polymerization is terminated.
- the unreacted gases which are then drawn from the autoclave contain 9 liters (standard conditions) of propylene.
- the catalyst is then decomposed by introducing methanol in the autoclave and the reaction product forming a solid mass soaked with gasoline and methanol is discharged.
- the polymer is purified by treatment with ether and hydrochloric acid in the heat and then coagulated completely with a large quantity of methanol. After filtration and hot drying under vacuum, the polymer amounts to 96 g. and consists of a white solid product which is fractionated by hot extraction with solvents.
- the acetone extract corresponds to 9.30% of the polymer obtained and consists of oily, low molecular weight products.
- the ether extract corresponds to 43.3% of the polymer obtained and consists of a rubbery, amorphous solid having in tetralin solutions at 135° C. an intrinsic viscosity of 0.8 (corresponding to a molecular weight of about 23,000).
- the heptane extract corresponds to 18.7% of the polymer obtained and consists of a partially crystalline solid having an intrinsic viscosity equal to 1 (corresponding to a molecular weight of about 32,000).
- the residue which remains after said extractions corresponds to 30.6% of the total polymer and consists of a powdery, highly crystalline solid having an intrinsic viscosity of 2.7 (corresponding to a molecular weight of about 150,000).
- the vinylhydrocarbon contains a small amount of ethylene, a copolymer results.
- Such copolymers have properties similar to those of the homopolymer.
- 5% of ethylene is mixed with the propylene or other vinylhydrocarbon, it is observed that the residual gases obtained after the polymerization has terminated are impoverished in the ethylene, indicating acceptance of ethylene into the polymer molecule.
- the properties of the polymeric products thus obtained are only slightly altered as compared to those of polypropylene or other polyvinylhydrocarbon,
- R may contain from 1 to 16 carbon atoms, and in specifically preferred embodiments may be an alkyl, cycloalkyl or aryl radical.
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Abstract
Description
TABLE I | ||||
Identity Period | x-ray | x-ray | ||
along the | melting | density | Density | |
Polymer | chain axis, Å | point ° C. | g/cc | by weight |
Polypropylene | 6.50 ± 0.05 | 160 | 0.94 | 0.92 |
Poly-alpha-butene | 6.70 ± 0.1 | 125 | 0.96 | 0.91 |
Poly-alpha-pentene | 6.60 ± 0.1 | 75 | — | 0.87 |
Polystyrene | 6.65 ± 0.05 | 230 | 1.12 | 1.08 |
The-x-rays densities were calculated for polystyrene and polybutylene on the basis of an hexagonal cell (Space-group R 3c or R 3c) having respectively a = 21.9 Å for polystyrene and 17.3 Å for polybutene. The cell contains 6 chain portions containing each 3 monomeric units. As no sufficient data is available to establish the correct unit cell of polypropylene, the x-ray density for this polymer was calculated by indexing the equatorial | ||||
# X-ray reflections on the basis of an oblique cell with a = 6.56 Å, b = 5.46 Å, = 106° C. 30′, and considering the identity period along the axis c = 6.5 Å |
TABLE 2 | ||||
1st order | 2nd order | Solubility in boiling |
transition | transition | measured | ethyl | ethyl | n-hep- | tolu- | ||
Polymer | temp. ° C. | temp. ° C. | density | Acetone | acetate | ether | tane | ene |
Crystalline | 155-165 | — | 0.92 | i | i | i | S.S. | S |
polypropylene | ||||||||
Amorphous | (−70°) | 0.85 | S.S. | S.S. | S. | S. | V.S. | |
polypropylene | ||||||||
Crystalline | 120-130 | — | 0.91 | i | i | i | S. | V.S. |
polybutene | ||||||||
Amorphous | — | — | 0.87 | S.S. | S.S. | S. | V.S. | V.S. |
polybutene | ||||||||
Crystalline | 70-80 | — | 0.87 | i | i | S.S. | S. | V.S. |
polypentene | ||||||||
Amorphous | — | — | — | S.S. | S.S. | S. | V.S. | V.S. |
polypentene | ||||||||
Crystalline | 210-230 | — | 1.08 | i | i | i | i | S. |
polystyrene | ||||||||
Amorphous | — | 80-90° | 1.05 | S.S. | S.S. | S. | S. | V.S. |
polystyrene | ||||||||
i = insoluble | ||||||||
S = soluble | ||||||||
VS = very soluble | ||||||||
SS = slightly soluble |
Claims (34)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/883,912 US6365687B1 (en) | 1954-06-08 | 1992-05-12 | Process for the polymerization and copolymerization of certain unsaturated hydrocarbons |
Applications Claiming Priority (14)
Application Number | Priority Date | Filing Date | Title |
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IT2422754 | 1954-06-08 | ||
IT24227 | 1954-06-08 | ||
IT25109 | 1954-07-27 | ||
IT2510954 | 1954-07-27 | ||
US51409755A | 1955-06-05 | 1955-06-05 | |
US51409955A | 1955-06-08 | 1955-06-08 | |
IT1152355 | 1955-08-06 | ||
US701332A US3112300A (en) | 1954-06-08 | 1957-12-09 | Isotactic polypropylene |
US71084058A | 1958-01-24 | 1958-01-24 | |
US49869983A | 1983-05-27 | 1983-05-27 | |
US90660086A | 1986-09-10 | 1986-09-10 | |
US60721590A | 1990-10-29 | 1990-10-29 | |
US71966691A | 1991-06-24 | 1991-06-24 | |
US07/883,912 US6365687B1 (en) | 1954-06-08 | 1992-05-12 | Process for the polymerization and copolymerization of certain unsaturated hydrocarbons |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US71966691A Continuation | 1954-06-08 | 1991-06-24 |
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Application Number | Title | Priority Date | Filing Date |
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US514098A Expired - Lifetime US3582987A (en) | 1954-06-08 | 1955-06-08 | Method for producing polymers and copolymers of certain unsaturated hydrocarbons |
US00514099A Expired - Lifetime US3715344A (en) | 1954-06-08 | 1955-06-08 | Regular linear head-to-tail polymerizates of certain unsaturated hydrocarbons and filaments comprising said polymerizates |
US602010A Expired - Lifetime US3175999A (en) | 1954-06-08 | 1956-08-03 | Block polymers of alpha-olefines, processes for producing the same, and mixtures thereof with isotactic polyolefines |
US701332A Expired - Lifetime US3112300A (en) | 1953-11-17 | 1957-12-09 | Isotactic polypropylene |
US07/883,912 Expired - Fee Related US6365687B1 (en) | 1954-06-08 | 1992-05-12 | Process for the polymerization and copolymerization of certain unsaturated hydrocarbons |
Family Applications Before (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US514098A Expired - Lifetime US3582987A (en) | 1954-06-08 | 1955-06-08 | Method for producing polymers and copolymers of certain unsaturated hydrocarbons |
US00514099A Expired - Lifetime US3715344A (en) | 1954-06-08 | 1955-06-08 | Regular linear head-to-tail polymerizates of certain unsaturated hydrocarbons and filaments comprising said polymerizates |
US602010A Expired - Lifetime US3175999A (en) | 1954-06-08 | 1956-08-03 | Block polymers of alpha-olefines, processes for producing the same, and mixtures thereof with isotactic polyolefines |
US701332A Expired - Lifetime US3112300A (en) | 1953-11-17 | 1957-12-09 | Isotactic polypropylene |
Country Status (11)
Country | Link |
---|---|
US (5) | US3582987A (en) |
BE (1) | BE550093A (en) |
CA (1) | CA1013497A (en) |
CH (1) | CH368623A (en) |
DE (3) | DE1094985B (en) |
DK (1) | DK111588B (en) |
FR (2) | FR1157793A (en) |
GB (2) | GB849106A (en) |
IT (1) | IT557911A (en) |
LU (1) | LU34560A1 (en) |
SE (1) | SE322052B (en) |
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Also Published As
Publication number | Publication date |
---|---|
DE1494189A1 (en) | 1970-03-12 |
FR1157793A (en) | 1958-06-03 |
DE1494188A1 (en) | 1970-10-15 |
CA1013497A (en) | 1977-07-05 |
LU34560A1 (en) | 1958-02-03 |
DE1494189B2 (en) | 1972-09-28 |
DE1094985B (en) | 1960-12-15 |
US3175999A (en) | 1965-03-30 |
DE1420559A1 (en) | 1968-10-10 |
CH368623A (en) | 1963-04-15 |
DE1494168B2 (en) | 1972-10-26 |
SE322052B (en) | 1970-03-23 |
DE1494168A1 (en) | 1970-01-02 |
FR1184072A (en) | 1959-07-16 |
DE1794361C2 (en) | 1974-02-28 |
US3715344A (en) | 1973-02-06 |
US3582987A (en) | 1971-06-01 |
DE1494188B2 (en) | 1973-01-04 |
IT557911A (en) | 1900-01-01 |
US3112300A (en) | 1963-11-26 |
GB849106A (en) | 1960-09-21 |
BE550093A (en) | 1957-02-04 |
DK111588B (en) | 1968-09-16 |
DE1794361B1 (en) | 1973-07-19 |
GB875132A (en) | 1961-08-16 |
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